Sulfur containing bis-phenolic compounds



United States Patent Ofi ice 3,489,804 SULFUR CONTAINING BIS-PHENOLIC COMPOUNDS Francis X. OShea, Naugatuck, Conn., assignor to Uniroyal, Inc., a corporation of New Jersey N Drawing. Filed Feb. 23, 1967, Ser. No. 617,856 Int. Cl. C07c 149/36 US. Cl. 260-609 9 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a series of bisphenolic compounds represented by the following formula:

The compounds of this invention are represented by the formula:

wherein R may be an alkyl group of one to eight carbon atoms or a cycloalkyl group of six to eight carbon atoms, where R may be an alkyl group of three to eight carbon atoms which is branched on the a-carbon, or a cycloalkyl group of six to eight carbon atoms, and Where X is a diradical containing from two to about thirty carbon atoms and is selected from the group consisting of:

(a) Polymethylene diradicals of the formula wherein n is a whole number from 2 to 30, for example:

CH2CH2-- and (CH2)30 (b) Branched chain polyalkylene dir adicals of the forwherein n is a whole number from 0 to 26 and the R groups may be hydrogen or alkyl groups and at least one of the R groups is an alkyl group, for example:

(c) Aralkyl diradicals of the formula Rn CH2- 3,489,804 Patented .Jan. 13, 1970 2 wherein R is an alkyl group of 1 to 4 carbon atoms and n is a whole number from 0 to 4, for example:

( d) Aralkyl diradioa-ls of the formulae:

(e) Aralkyl diradicals of the formulae:

(f) Cyclic hydrocarbon containing diradicals of the general formula:

lllor sil wherein R may be hydrogen or an alkyl group and n is a whole number from 0 to 6, for example and CH3 H3 I (5 CH3 CH and CH (g) Aliphatic diradicals containing hetero atoms of the general formula:

wherein R may be hydrogen or alkyl, n is a whole number from l-to 6 and Z is selected from the group consisting of -O, S-, SO and NR- (wherein R is an alkyl group), for example, -CH CH OCH CH- and (h) Diradicals of the formulae:

-CH CH OCH CH OCH CH and CH CH OCH OCH CH (i) Aralkyl diradicals of the general formula:

wherein R may be hydrogen or an alkyl group, for example:

CH4 CH3 (j) Diradic-als of the formula:

wherein Ri's an alkyl group of 1 to 5 carbon atoms.

(k) The diradical ofthe formula:

The compounds of my invention may be prepared by one of two general methods.

Method A'.-This method involves the reaction of two molar equivalents of a mercaptophenol of the general formula:

in which R and R are as previously described with two molar equivalents of an alkali metal hydroxide, e.g sodium hydroxide and potassium hydroxide, and one molar equivalent of an organic dihalide of the formula:

Hal--X-Hal in which Hal represents a halogen atom and X is as previously described. The following equation illustrates a preparation of this type:

The reaction may be carried out in a suitable water miscible solvent such as methanol, ethanol, isopropanol, dioxane, ethylene glycol dimethyl ether, etc. at a temperature from about room temperature to about 100 C.

Preferred solvents for the reaction are methanol, ethanol and isopropanol. The preferred temperature is in the range of 50 C. to 100 C., the reaction ordinarily being carried out at or near the reflux temperature of the solution. The preferred time of the reaction is up to four hours. Longer times may be used but are not necessary, the reaction generally being complete in 30 minutes or less.

The reaction may also be carried out in a two-phase system such as benzene-water or xylene-water, using vigorous agitation. Although longer reaction times are generally employed than in homogenous solution, this heterogeneous system has the advantage of providing a simplified recovery procedure. In-such a two-phase system the product is soluble in the organic phase which can be readily separated from the aqueous phase containing the alkali metal halide. The product is finally obtained by removing the solvent from the organic phase.

Method B.-T.his method involves the reaction of two 4 molar equivalents of a mercaptophenolof the general formula:

I: SH

in which R and R are as previously described, with one molar equivalent of a non-conjugated diolefin of from 5 to 30 carbon atoms under acid catalysis. The following equation illustrates a preparation of this. type:

This reaction may be carried out without a solvent or in a non-polar organic solvent such as hexane, benzene, xylene, etc. at a temperatureup to about C. The acid catalyst which may be employed includes, but is not limited to, mineral acids, such as sulfuric acid, hydrochloric acid, AlCl and BF and heterogeneous catalysts such as acid clays and acidic ion exchange resins.

Some of the diolefinswhich may be used include:

Para-diisopropenyl benzene, Meta-diisopropenyl benzene, Divinyl benzene,

Vinyl isopropenyl benzene, 1,7-octadiene,

Vinyl cyclohexene, 1-methyl-4-isopropenyl cyclohexene-l, 1,4-hexadiene,

1 13 -tetradecadiene 2,7-dimethy1-1,7-octadiene, 'Ethylidene norbornene and Isopropylidene norbornene.

Some of the mercaptophenols which may, be. used include:

2,6-diisopropyl-4-mercaptophenol, 2-met-hyl-4-mercapto-6-t-butylphenol, 2,6-di-sec-butyl-4-mercaptophenol, 2,6-di-t-butyl-4-mercaptophenol, 2-methyl-4-mercapto-6-cyclohexylphenol, 2,6-dicyclohexyl-4-mercaptophenol, Z-methyl-4-mercapto-6-cyclooctylphenol, 2,6-dicyclooctyl-4-mercaptophenol, 2Pmethyl-4-rn'ercapto-6-(a-methylheptyDphenol, 2,6-di( a-methylheptyl) -4-mercaptophenol and 2,6-di-t-octyl-4-mercaptophenol.

The novel compounds disclosed-herein have previously been unreported, and such compounds are set forth for the first time. In US. Paent No. 2,472,318 issued June 7, 1949 to Philip Subkow, compounds of the following formula were disclosed:

wherein R is selected from the group consisting of an aryl, alkylaryl, substituted aryl, alkylaryl groups, S is sulfur and R' is a low molecular weight alkyl group. These compounds are disclosed as possessing activity as oxidation inhibitors for lubricating oils. Among the possible structures set forth by Subkow was included the following compound, which is considered the closest prior art uncovered:

CH3 H3 My contribution differs from the prior art in that the compounds of the instant invention contain two alkyl groups on each benzene ring, both being in the ortho position with relation to the phenolic hydroxyl groups. In addition, at least one alkyl group on each ring is branched on the alpha carbon atom. The prior art does not describe any alkyl group longer than methyl, does not describe any compound with two-alkyl groups on each benzene ring and does not exhibit an alkyl group in the ortho position with relation to the phenolic hydroxy] groups.

Furthermore, the prior art compounds of Subkow are never credited with antioxidant activity in the preparation of olymers; while the compounds of my invention display excellent antioxidant activity for various polymer systems, e.g. rubber and plastics.

To illustrate the novel bis-phenol compounds and their methods of preparation, the following examples are given. In the examples, the proportions are expressed in parts by weight unless otherwise noted.

Example 1 V The preparation of 1,4 bis(3-methyl-4-hydroxy-5-tbutylphenylthio)-butane.

To a solution of 9.8 g. (0.05 mole) of 2-methyl-4-mercapto-6-t-butylphenol and 4 g. (0.05 mole) of 50% aqueous sodium hydroxide in 75 m1. of ethanol was added 3.2 g. (0.025 mole) of 1,4-dichlorobutane. The reaction mixture was refluxed gently for 15 minutes. The solution was then poured into cold water and the product was extracted with ether. The ether extract was washed with water, dried over anhydrous sodium sulfate and evaporated down to a solid residue which was recrystallized from hexane yielding 9 g. (80% yield) of 1,4-bis(3- methyl 4 hydroxy 5 t butylphenolthio)butane, M.P. 80-82.

Analysis.Calcd for C H O S percent C, 69.90; percent H, 8.52; percent S, 14.30.

Found: percent C, 69.65; percent H, 8.54; percent S, 14.54. p

ExampleZ The preparation of 1,2 bis( 3 methyl 4 hydroxy 5 t butylphenylthio) -ethane.

2 methyl 4 mercapto 6 t butylphenol was reacted with ethylene dichloride in the manner described in Example 1 to give a 77% yield of 1,2 bis(3 methyl 4 hydroxy 5 t butylphenylthio)ethane, M.P. 142- 144 C. Analysis.-Calcd for C H Q S percent C, 68.90; percent H, 8.14; percent S, 15.30.

Found: percent C, 68.84; percent H, 8.11; percent S, 15.68.

Example 3 The preparation of 1,2 bis(3,5 di t hydroxyphenylthio)ethane.

2.6- di t butyl 4 mercaptophenol was reacted with ethylene dichloride in the manner described in Example 1 to yield 1,2 bis(3,5 di t butyl -4 hydroxyphenylthio) ethane, M.P. 158-159 after recrystallization from methanol.

Analysis.-Calcd for C H O S percent C, 71.71; percent H, 9.16; percent S, 12.74.

Found: percent C, 71.89; percent H, 9.20; percent S, 12.74. i

butyl 4.

. with 1,4 dichlorobutane in the manner described in Example 1 to yield 1,4 bis(3,5-di-t-butyl-4-hydroxyphenylthio)butane, M.P. 137-140.

Analysis.-Calcd for C H O S percent C, 72.45; percent H, 9.43; percent S, 1230.

Found: percent C, 72.28; percent H, 9.51; percent S, 12.37.

Example 5 Example 6 The preparation of 0:,oc' bis( 3 methyl 4 hydroxy- 5 t butylphenylthio) p xylene.

2 methyl 4 mercapto 6 t butylphenol was reacted "with 04,11 dichloro p xylene in the manner described in Example 1 to yield 01,06 bis(3 methyl 4 hydroxy 5 t butylphenylthio) p xylene, M.P. 112.

Analysis.-Calcd for C H O S percent C, 73.0; percent H, 7.70; percent S, 13.0.

Found: percent C, 73.22; percent H, 7.75; percent S, 13.20.

Example 7 The preparation of 3,5 bis(3 methyl 4 hydroxy- 5 t butylphenylthio)diethyl ether.

2 methyl 4 mercapto 6 t butylphenol was reacted with 8, 3 dichlorodiethyl ether in the manner described in Example 1 to give 3,18 bis(3 methyl 4 hydroxy 5 t butylphenylthio) diethyl ether as a viscous oil.

Example 8 The preparation of a bis[3 methyl 4 hydroxy- 5 t butylphenylthio] p diisopropylbenzene.

To a solution of 19.6 g. (0.1 mole) of 2 methyl 4 mercapto 6 t butylphenol and 7.9 g. (0.05 mole) of p diisopropenyl benzene in 20 ml. of benzene was added 4 g. of KSFO activated montmorillonite catalyst. The mixture was heated on the steam bath overnight. It was then filtered and evaporated down to yield a,u' bis( 3 methyl 4 hydroxy 5 t butylphenylthio) p diisopropyl benzene as a viscous oil.

Example 9 The preparation of l-methyl-l-(3-methyl-4-hydroxy-S- t butylphenylthio) [u (3 methyl-4-hydroxy-S-t-butyl phenylthio)isopropyl]cyclohexane.

In the same manner as described in Example 8, 9.8 g. (0.05 mole) of Z-methyl-4-mercapto-6-t-'buty1pheno1 was reacted with 3.4 g. (0.025 mole) of d-limonene using 1 g. of KSFO catalyst. The product was obtained as a viscous oil.

Example 10 The preparation of 2,7-bis(3-methyl-4-hydroxy-5-tbutylphenylthio octane.

In the same manner as described in Example 8, 9.8 g. (0.05 mole) of 2-methyl-4-mercapto6-'t-butylphenol was reacted with 2.8 g. (0.025 mole) of 1,7-octadiene using 0.5 g. of KSFO catalyst. The product was obtained as a viscous oil.

7 Example 11 The preparation of 4,8bis(3,5-di-sec-buty1-4-hydroxyphenylthio)-tricyclo[ 2 1 0 decane.

In the same manner as described in Example 8, 11.8 g. (0.05 mole) of 2,6-di-secbutyl-4-mercaptophenol was reacted with 3.3 g. (0.025 mole) of dicyclopentadiene using 1 g. of KSFO catalyst. The product was obtained as a viscous oil.

Example 12 The preparation of 1-[a-(3,5-dicyclooctyl-4-hydroxyphenylthio)ethyl] 4 (3,5 dicyclooctyl-4-hydroxyphenylthio bicyclo [2 2 1 heptane.

In the same manner as described in Example 8, 17.3 g. (0.05 mole) of 2,6-dicyclooctyl-4 mercaptophenol was reacted with 3.0 g. (0.025 mole) of ethylidene norbornene using 1 g. of KSFO catalyst. The product was obtained as a viscous oil.

I claim:

1. A chemical of the formula:

wherein R is selected from the group consisting of an alkyl group of 1-8 carbon atoms and a cycloalkyl group of 6-8 carbon atoms and wherein R is selected from the group consisting of an alkyl group of 3-8 carbon atoms branched on the a carbon atom and a cycloalkyl group of 6-8 carbon atoms and wherein X is a diradical containing from 2-30 carbon atoms and is selected from the group consisting of:

(a) polymethylene diradicals of the formula (CI-12):":- wherein n is a whole number from 2 to 8; (b) branched chain polyalkylene diradicals of the formula:

CHr-

R CH2- wherein R is an alkyl group of 1 to 4 carbon atoms and n' is a whole number from 0 to 4; (d) aralkyl diradicals of the formulae:

CH2- and (e) aralkyl diradicals of the formulae:

and

(f) cyclic hydrocarbon containing diradicals of the general formula:

ill. ZRlZL \I i/n CRz-Cz 0 wherein R may be hydrogen or an alkyl group of up to 6 carbon atoms, and It is a whole number from 0 to 6:

(g) aliphatic diradicals containing hetero atoms of the general formula \l/. W. wherein R may be hydrogen or alkyl group of up to 6 carbon atoms, n is a whole number from 1 to 6 and Z may be -O, S, SO (h) diradicals of the formulae:

CH CH OCH CH OCH CH and CH CH -OCH -OCH CH (i) aralkyl diradicalsof the general formula:

CH3 \l wherein R is selected from the group consisting of hydrogen and an alkyl group of from 1-12 carbon atoms.

(j) diradicals of the formula:

wherein R is an alkyl group of l to 5 carbon atoms, (k) the diradical of the formula:

' 2. A chemical of claim 1, wherein R is an alkyl group of from 1 to 8 carbon atoms, R; is an alkyl group of from 3 to 8 carbon atoms and X is ethane.

3. 1,4 bis(3 methyl 4-hydroxy-S-t-butylphenylthio) butane.

4. 1,2 bis(3 methyl 4-hydroxy-5-t-butylphenylthio) ethane.

. 5. 1,2 bis(3,5 di t-butyl- 4 hydroxyphenylthio) ethane.

6. 1,2 bis(3,5 diisopropyl 4 hydroxyphenylthio) ethane. Y

7. ,0! bis(3 methyl 4 hydroxy 5 t-butylphenyl thio)-p-xylene.

8. an bis(3 methyl 4 hydroxy 5 t butylphenyl thio)-diethyl ether.

9. ot,a' bis(3 methyl 4 hydroxy 5 t butylphenyl thio)-p-diisopropylbenzene.

References Cited Ipatiefi et al.: J. Amer. Chem. Soc., vol. (1938), pp. 2731-34. Galt et al.: J. Chem. Soc. (1959). Vander Ploeg et a1.: Rec. Trav. Chem, vol. 81 (1962), pp. 775-785.

CHARLES B. PARKER, Primary Examiner D. R. PHILLIPS, Assistant Examiner 1 US. Cl. X.R. 252-402, 404; 260-459, 45.95, 570.5

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3:u89:8on Dated January 13, 1970 Inventofls) Francis X. O'Shea It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The formula in Claim 1 part (0) should read:

SI'GNED AN'D SEALED JUL 1 41970 Atteal:

Edward M. Fletcher. In

I WILLIAM E. SGHUYIIER, JR. Attesung Officer Comissioner of Patents 

